AlN/GaN multiple quantum wells (MQWs) were grown on sapphire substrates by plasmaassisted molecular beam epitaxy. Growth temperature, III/V ratio, growth rate, and other growth parameters were optimized for the buffer layer and the MQWs, separately. The growth of AlN buffer was kept as Al-rich as possible while the formation of Al droplets was avoided. A GaN buffer layer was also tried but proved to be inferior to AlN buffer probably due to its larger surface roughness, higher dislocation density, and larger lattice mismatch with the AlN barrier layers in the MQWs. Very flat surfaces with a RMS roughness of 0.7nm were observed by atomic force microscopy (AFM) on the samples with both AlN buffer layer and 20 MQWs deposited under the optimized growth conditions. Abrupt interfaces and excellent periodicities of the MQWs were confirmed by X-ray diffraction (XRD) and reflectivity measurements with MQWs' satellite peaks clearly visible up to the 10th order. Room-temperature intense ultraviolet (UV) photoluminescence (PL) emission with wavelength in the range of 320–350nm was also observed from the MQWs with well width ranging from 1.0 to 1.5nm. These MQW structures can potentially be used for UV light emitters and quantum cascade lasers.